This invention relates to electrochemical fuel cells, more particularly electrochemical fuel cells which employ hydrogen as a fuel and receive an oxidant to convert the hydrogen to electricity and heat. This invention is even more particularly concerned with the humidification requirements of such an electrochemical fuel cell employing a proton exchange membrane.
Generally, a fuel cell is a device which converts the energy of a chemical reaction into electricity. It differs from a battery in that the fuel cell can generate power as long as the fuel and oxidant are supplied.
A fuel cell produces an electromotive force by bringing the fuel and oxidant into contact with two suitable electrodes and an electrolyte. A fuel, such as hydrogen gas, for example, is introduced at a first electrode where it reacts electrochemically in the presence of the electrolyte and catalyst to produce electrons and cations in the first electrode. The electrons are circulated from the first electrode to a second electrode through an electrical circuit connected between the electrodes. Cations pass through the electrolyte to the second electrode. Simultaneously, an oxidant, typically air, oxygen enriched air or oxygen, is introduced to the second electrode where the oxidant reacts electrochemically in presence of the electrolyte and catalyst, producing anions and consuming the electrons circulated through the electrical circuit; the cations are consumed at the second electrode. The anions formed at the second electrode or cathode react with the cations to form a reaction product, such as water. The first electrode or anode may alternatively be referred to as a fuel or oxidizing electrode, and the second electrode may alternatively be referred to as an oxidant or reducing electrode. The half-cell reactions at the two electrodes are as follows:
First Electrode: H2xe2x86x922H++2exe2x88x92
Second Electrode: xc2xdO2+2H++2exe2x88x92xe2x86x92H2O
The external electrical circuit withdraws electrical current and thus receives electrical power from the cell. The overall fuel cell reaction produces electrical energy which is the sum of the separate half-cell reactions written above. Water and heat are typical by-products of the reaction.
In practice, fuel cells are not operated as single units. Rather, fuel cells are connected in series, stacked one on top of the other, or placed side by side. A series of fuel cells, referred to as fuel cell stack, is normally enclosed in a housing. The fuel and oxidant are directed through manifolds to the electrodes, while cooling is provided either by the reactants or by a cooling medium. Also within the stack are current collectors, cell-to-cell seals and insulation, with required piping and instrumentation provided externally to the fuel cell stack. The stack, housing, and associated hardware make up the fuel cell module.
Fuel cells may be classified by the type of electrolyte, which is either liquid or solid. The present invention is primarily concerned with fuel cells using a solid electrolyte, such as a proton exchange membrane (PEM). The PEM has to be kept moist with water because the available membranes will not operate efficiently when dry. Consequently, the membrane requires constant humidification during the operation of the fuel cell, normally by adding water to the reactant gases, usually hydrogen and air.
The proton exchange membrane used in a solid polymer fuel cell acts as the electrolyte as well as a barrier for preventing the mixing of the reactant gases. An example of a suitable membrane is a copolymeric perfluorocarbon material containing basic units of a fluorinated carbon chain and sulphonic acid groups. There may be variations in the molecular configurations of this membrane. Excellent performances are obtained using these membranes if the fuel cells are operated under fully hydrated, essentially water-saturated conditions. As such, the membrane must be continuously humidified, but at the same time the membrane must not be over humidified or flooded as this degrades performances. Furthermore, the temperature of the fuel cell stack must be kept above freezing in order to prevent freezing of the stack.
Cooling, humidification and pressurization requirements increase the cost and complexity of the fuel cell, reducing its commercial appeal as an alternative energy supply in many applications. Accordingly, advances in fuel cell research are enabling fuel cells to operate without reactant conditioning, and under air-breathing, atmospheric conditions while maintaining usable power output.
The current state-of-the-art in fuel cells, although increasingly focusing on simplified air-breathing, atmospheric designs, has not adequately addressed operations in sub-zero temperatures, which requires further complexity in the design. For instance, heat exchangers and thermal insulation are required, as are additional control protocols for startup, shut-down, and reactant humidifiers.
Where a solid polymer proton exchange membrane (PEM) is employed, this is generally disposed between two electrodes formed of porous, electrically conductive material. The electrodes are generally impregnated or coated with a hydrophobic polymer such as polytetrafluoroethylene. A catalyst is provided at each membrane/electrode interface, to catalyze the desired electrochemical reaction, with a finely divided catalyst typically being employed. The membrane/electrode assembly is mounted between two electrically conductive plates, each which has at least one fluid flow passage formed therein. The fluid flow conductive fuel plates are typically formed of graphite. The flow passages direct the fuel and oxidant to the respective electrodes, namely the anode on the fuel side and the cathode on the oxidant side. The electrodes are electrically connected in an electric circuit, to provide a path for conducting electrons between the electrodes. In a manner that is conventional, electrical switching equipment and the like can be provided in the electric circuit as in any conventional electric circuit. The fuel commonly used for such fuel cells is hydrogen, or hydrogen rich reformate from other fuels (xe2x80x9creformatexe2x80x9d refers to a fuel derived by reforming a hydrocarbon fuel into a gaseous fuel comprising hydrogen and other gases). The oxidant on the cathode side can be provided from a variety of sources. For some applications, it is desirable to provide pure oxygen, in order to make a more compact fuel cell, reduce the size of flow passages, etc. However, it is common to provide air as the oxidant, as this is readily available and does not require any separate or bottled gas supply. Moreover, where space limitations are not an issue, e.g. stationary applications and the like, it is convenient to provide air at atmospheric pressure. In such cases, it is common to simply provide channels through the stack of fuel cells to allow for flow of air as the oxidant, thereby greatly simplifying the overall structure of the fuel cell assembly. Rather than having to provide a separate circuit for oxidant, the fuel cell stack can be arranged simply to provide a vent, and possibly some fan or the like to enhance air flow.
Catalytic burners are also known and operate on a principle similar to fuel cells, but at an accelerated kinetic rate and increased temperature. A fuel, for example hydrogen, is oxidized through direct contact with oxygen or air at a rate induced by the presence of a catalytic bed, for example, ceramic beads containing small amounts of platinum on the surface.
The by-product of the chemical reaction is similar to that of a fuel cell, but without any generation of electricity:
O2+2H2xe2x86x922H2O+HEAT
The higher consumption rate of the reactants and concomitant heat release reflects the fact that the reaction occurs through direct contact rather than through a proton/electron transaction. Catalytic burning is flameless, and occurs at a temperature between that of a fuel cell""s xe2x80x9ccold combustionxe2x80x9d and that of an open-flame combustion. Flow rate can be pulsed or modulated to achieve varying heat and moisture profiles. Hydrogen catalytic burning requires no pilot flame or spark to be initiated.
An example of a proposal for a catalytic burner is found in an article entitled xe2x80x9cCatalytic Combustion of Hydrogen in a Diffusive Burnerxe2x80x9d by K. Stephen and B. Dahm at pages 1483-1492 of Catalytic Combustion of Hydrogen in a Diffusive Burner.
In the prior art, humidification through membrane stack provided humidification only, without imparting significant temperature shift. In the present invention, both humidification and temperature are imparted to the stream prior to admission to the stack.
In accordance with a first aspect of the present invention, there is provided a tubular reactor, for catalyzing reaction of hydrogen and a gaseous oxidant, the tubular reactor comprising:
an elongated housing, a catalyst formed from a material adapted to promote catalytic combustion of the fuel and the oxidant, being formed into an elongated body substantially filling the elongate housing and being porous, a first inlet for a gaseous fuel and a second inlet for a gaseous oxidant, both first and second inlets being provided at one end of the elongated housing;
and an outlet at the other end of the housing, whereby, in use, the catalyst promotes combustion between the fuel and the oxidant to generate heat and moisture, whereby a heated and humidified gas flow exits through the outlet.
Preferably, the housing and the body of the catalyst are both generally cylindrical and have length substantially longer than the diameter than the tubular reactor.
In accordance with a second aspect of the present invention, there is provided a fuel cell system comprising at least one fuel cell, each fuel cell comprising:
an inlet for a fuel;
an anode having a catalyst associated therewith for producing cations from the fuel;
a fuel manifold, connected between the inlet and the anode, for distributing fuel to the anode;
an oxidant inlet means for supplying oxidant;
a cathode having a catalyst associated therewith and connected to the oxidant inlet means, for producing anions from the oxidant, said anions reacting with said cations to form water on said cathode;
an ion exchange membrane deposed between said anode and said cathode, said membrane facilitating migration of cations from said anode to said cathode, while isolating the fuel and the oxidant from one another;
a catalytic reactor having a first inlet for fuel and a second inlet for an oxidant, and an outlet for heated and humidified gas, the catalytic reactor being mounted to supply the heated and humidified gas to the fuel cell.
Preferably, the fuel cell system comprises a plurality of fuel cells, forming a fuel cell stack.
The stack can comprise an air-breathing stack, including a plurality of channels extending through the fuel cell stack for permitting free flow of ambient air as the oxidant through the fuel cell stack, there being at least one channel for each fuel cell, wherein the catalytic reactor is mounted below the fuel cell stack. The catalytic converter is configured to receive air as an oxidant through the second inlet thereof in excess of the stoichiometric quantity of air required for combustion of fuel within the catalytic reactor, whereby heated and humidified air is discharged from the outlet of the catalytic reactor. The outlet of the catalytic reactor is mounted below the channels of the fuel cell stack, whereby heated and moistened air flows upwardly through the channels of the fuel cell stack from the catalytic reactor.
The catalytic reactor can be either generally tubular or it can be disk-shaped, configured for flow of fuel and oxidant generally along the central axis of the reactor.
A further aspect of the present invention provides a method of operating a fuel cell system comprising a plurality of fuel cells, each fuel cell comprising an inlet for fuel, an anode having a catalyst associated therewith for producing cations from fuel, a fuel manifold connected between the inlet and the anode for distributing fuel to the anode, an oxidant inlet means for supplying oxidant, a cathode having a catalyst associated therewith and connected to the oxidant inlet means for producing anions from the oxidant, said anions reacting with said cations to form water on said cathode and an ion exchange membrane disposed between the anode and the cathode, for facilitating migration of cations from the anode to the cathode, while isolating the fuel and oxidant from one another, the method comprising
(a) supplying oxidant and fuel to the fuel cell for reaction to generate electrical power and heat;
(b) supplying fuel to the catalytic reactor and oxidant to the catalytic reactor, in an amount greater than the stoichiometric amount required for the combustion of the fuel, to ensure complete combustion of the fuel, thereby generating a flow of heated and humidified oxidant;
(c) supplying the heated and humidified oxidant to the fuel cell, for reaction with the fuel to generate electricity and heat.
For initial start-up below a preset temperature, the method can comprise initially supplying fuel and oxidant only to the catalytic reactor to generate a flow of heated and moistened oxidant, and passing the heated and moistened oxidant through the fuel cell to preheat the fuel cell, and commencing supply of fuel to the fuel cell, once the fuel cell reaches a desired temperature. Then, after start-up and after the fuel cell has reached the desired temperature, a sufficient quantity of the oxidant and the fuel are supplied to the reactor, to maintain the oxidant supplied to the fuel cell system at a desired humidity level.
Yet another aspect of the present invention provides a method of operating a fuel cell system comprising a plurality of fuel cells, each fuel cell comprising an inlet for fuel, an anode having a catalyst associated therewith for producing cations from fuel, a fuel manifold connected between the inlet and the anode for distributing fuel to the anode, an oxidant inlet means for supplying oxidant, a cathode having a catalyst associated therewith and connected to the oxidant inlet means, for producing anions from the oxidant, said anions reacting with said cations to form water on said cathode and an ion exchange membrane disposed between the anode and the cathode, for facilitating migration of cations from the anode to the cathode, while isolating the fuel and the oxidant from one another, the method comprising:
(a) supplying oxidant and fuel to the fuel cells for reaction to generate electrical power and heat;
(b) supplying fuel to the catalytic reactor and oxidant to the catalytic reactor, in an amount less than the stoichiometric amount required for combustion of fuel, to ensure complete consumption of the oxidant, thereby generating a flow of heated and humidified fuel;
(c) supplying the heated and humidified fuel to the fuel cell, for reaction with oxidant known to generate electricity and heat.
This aspect of the method can include:
(a) providing a second catalytic reactor;
(b) supplying the second reactor with fuel and oxidant in an amount greater than the stoichiometric amount required for combustion of fuel, thereby generating a flow of heated and humidified oxidants; supplying the heated and humidified oxidant to the oxidant inlet means of the fuel cell, for reaction with a heated and humidified fuel to generate electricity and heat. In the prior art, humidification through membrane stacks provided humidification only, without imparting a significant temperature shift. In this invention, both humidity and temperature are imparted to the stream prior to admission to the stack.